Insecticidal compositions of matter and method of preparation therefor



ilnited @tates Patent Ofifice 3,56,793 Patented Oct. 2, 1952 3,356,793 HJSECTECHBAL tIOh iPUSiHONS OF h IATTCER AND METHOD Old PEEFARATlfiN THEREFOR John P. Ln'tisi, Peri: Ridge, liiL, assignor to Universal Oil Products Company, Des l iaines, ilL, a corporation of Delaware No Drawing. Filed Dec. 27, 1%0, Ser. No. 78,216 17 Claims. (Cl. Zed-4%) This invention relates to novel compositions of matter which may be employed as insecticides and to a method for the preparation thereof. More particularly the invention is concerned with a process for condensing halo substituted alkadienes or cycloaliiadienes with alkyl heterocyclic compounds in the presence of a decomposing peroxide.

One object of this invention resides in a process for condensing halo substituted unsaturated compounds with alkyl heterocyclic compounds in the presence of a decomposing peroxide to form novel compositions of matter which possess insecticidal properties.

A further object or" this invention is found in a process for condensing halo conjugated alkadienes or halo conjugated cycloalkadienes with a substituted alkyl heterocyclic compound in the presence of a decomposing peroxide to form insecticidal compositions of matter.

One embodiment of this invention resides in a process which comprises condensing a halo substituted compound selected from the group consisting of chloro substituted alkadienes and chloro substituted cycloalkadienes with an alkyl heterocyclic compound in the presence of a catalyst comprising a decomposing peroxy compound at condensation conditions, and recovering the resultant condensation product.

A further embodiment of this invention is found in a process which comprises condensing a chloro substituted compound selected from the group consisting of chloro substituted alkadienes and chloro substituted cycloalkadienes in which at least one chlorine atom is attached to each of a pair of doubly bonded carbon atoms with an alkyl heterocyclic compound in the presence of a catalyst comprit .ng a decomposing peroxy compound at a temperature at least as high as the decomposition temperature of said peroxy compound, and recovering the resultant condensation product.

Yet another embodiment of this invention is found in a process which comprises condensing a halo substituted compound selected from the group consisting of chloro substituted alkadienes and chloro substituted cycloalkadienes with Z-methylthiophene in the presence of a catalyst comprising a decomposing peroxy compound at a temperature at least as high as the decomposition temperature of said peroxy compound, and recovering the resultant condensation product.

A specific embodiment of this invention is found in a process which comprises condensing hexachlorocyclopentadiene with 2-methylthiophene in the presence of di-tbutyl peroxide at a temperature in the range of from about 130 to about 150 C., and recovering the resultant pentachloro-(Z-thenyl)-l,3-cyclopentadienes.

Yet another embodiment of this invention resides in a compound selected from the group consisting of chloro substituted alkadienic and chloro substituted cycloalkadienic derivatives of an alkyl heterocyclic compound.

Another specific embodiment of this invention resides in pentachloro- Z-thenyl l ,3 -cyclopentadienes.

Other objects and embodiments referring to alternative chloro substituted conjugated alkadienes, chloro substituted conjugated cycloalkadienes, alkyl heterocyclic compounds and decomposing peroxides will be found in the following further detailed description of this invention.

It has now been found that certain chloro substituted alkadienes or chloro substituted cycloalkadienes namely those in which at least one halogen atom is attached to each of a pair of doubly bonded carbon atoms may be condensed with an alkyl heterocyclic compound or a substituted alkyl heterocyclic compound in which the substituents are positioned on the nucleus of the heterocyclic ring, in the presence of a decomposing peroxide catalyst at a temperature at least as high as the decomposition temperature of the catalyst, to form compositions of matter which possess insecticidal properties. For example, hexachlorocyclopentadiene may be condensed with Z-methylthiophene to form 2,3,4,5,5-pentachloro-l-(Z-thenyl)-l,3-cyclopentadiene, 1,2,3,4,5 pentachloro-5-(2-thenyl)-l,3-cyclopentadiene and 1,3,4,5,5-pentachloro-2-(2-thenyl)-1,3-cyclopentadiene which will possess insecticidal activity, especially against housefiies. In addition to possessing insecticidal activity the compounds formed by the process of this invention will also find a wide variety of uses in the chemical field, particularly being used as intermediates in the preparation of resins, pharmaceuticals, plastics, etc.

Unsaturated chlorinated compounds containing only carbon, hydrogen and halogen atoms which may be reacted with the nuclearly substituted alkyl aromatic compound in the process of the present invention include straight chain halogenated conjugated alkadienes having the general formula 01 C1 X X in which each of the X radicals is independently selected from the group consisting of hydrogen and chlorine radicals and each of the R radicals is independently selected from the group consisting of hydrogen, alkyl, halo and haloalkyl radicals containing from 1 to 6 carbon atoms, or polyhalocycloalkadienes containing only carbon, hydrogen and halogen atoms having the general formula:

in which X is independently selected from the group consisting of hydrogen, alkyl, halo and haloalkyl radicals. Examples of these compounds include haloalkadienes such as 1,2-dichloro-l,3-butadiene, 1,2,3-trichloro-1,3-butadiene, 1,2,3,4 tetrachloro-1,3-butadiene, hexachloro 1,3- butadiene, 2,3,4,5-tetrach1oro-2,4-hexadiene, etc.; 1,2-dichloro-1,3-pentadiene, 1,2,3-trichloro-l,3-pentadiene, 1,2, 3,4-tetrachloro-l,3-pentadiene, 1,2-dichloro-1,3-hexadiene, 1,2,3-trichloro-l,3-hexadiene, etc.; and halocycloalkadicues, such as halogenated 1,3-cyclopentadienes which for purposes of this invention will be designated as halogenated cyclopentadienes including 1,2-dichloro-cyclopentadiene, 1,2,5-, 1,2,4-, 1,4,5-, or 1,2,3-trichlorocyclopentadiene, 1,2,3,5-, 1,2,4,5-, 1,2,3,4-, or 1,2,5,5-tetrachlorocyclopentadiene, 1,2,3,5,5'- 1,2,4,5,5- or l,2,3,4,5-penta chlorocyclopentadiene, hexachlorocyclopentadiene, 1,2-dichloro-1,3-cyclohexadiene, 1,2,3 trichloro-l,3-cyclohexadiene, 1,2,3,4-, 1,2,3,5-, 1,2,3,6-tetrachloro-1,3-cyclohexadiene, l,2,3,4,5-pentachloro-l,S-cyclohexadiene, 1,2,3,4,5, 5-, l,2,3,4,5,6-, and 1,2,3,4,6,6-hexachloro-1,3cyclohexadiene, heptachloro-1,3-cyclohexadiene, octachloro-1,3-cyclopentadiene, 1,2-dichlorol ,4-cyclohexadiene, 1,2,3-trichloro-1,4-cyclohexadiene, l,2,3,4-, 1,2,3,5-, 1.,2,3,6-tetrachloro-1,4-cyclohexadiene, isomeric penta-, hexa-, heptaand octa-chloro-l,4'cyclohexadienes. In addition, it is also contemplated that polyhaloalkadienes and polyhalocycloalkadienes which are used in this process may contain more than one species of halo substitutents, such as,

for example, l,2-dichloro-3-fluoro-1,3-butadiene, 1,4-difluoro-l,2,3,4-tetrachloro-l,3-butadiene, l,4-dibromo-l,2, 3,4-tetrachloro 1,3 butadiene, 1,4-diiodo-1,2,3,4-tetrachloro-l,3-butadiene, 5,5-difiuoro-5,5-dibromoand 5,5-diiodo-l,2,3,4 tetrachloro-l,3-cyclopentadiene, etc., may also be used although not necessarily with equivalent results.

Examples of alkyl substituted heterocyclic compounds which may be condensed with the chloro substituted conjugated alkadienes or chloro substituted conjugated cycloalkadienes according to the process of this invention possess the generic formula in which Z is selected from the group consisting of sulfur, oxygen and nitrogen atoms, R is independently selected from the group consisting of hydrogen, alkyl, aryl, amino, nitro and alkoxy radicals, at least one R being an alkyl radical of from 1 to 4 carbon atoms and n is an integer of from 1 to 2. Specific examples of these compounds include Z-methylthiophene, 2-ethylthiophene, 2-propylthiophene, 2-butylthiophene, 2,3-dimethylthiophene, 2,3-diethylthiophene, 2,3-dipropylthiophene, 2,3-dibutylthiophene, 2,5-dimethylthiophene, 2,5-diethylthiophene, 2,5-dipropylthiophene, 2,5-dibutylthiophene, 2,3,S-trimethylthiophene, 2,3,S-triethylthiophene, 2,3,S-tripropylthiophene, 2,3,5- tributylthiophene, 2-methyl-3-methoxythiophene, 2-ethyl- S-methoxythiophene, 2-propyl 3 methoxythiophene, 2- butyl-3-rnethoxythiophene, 2-rnethyl-3-ethoxythiophene, 2- ethyl-3-ethoxythiophene, 2-propy1-3-ethoxythiophene, 2- butyl-3-ethoxythiophene, 2-ethyl-4-methoxythiophene, 2- propyl-4-rnethoxythiophene, 2-butyl-4-methoxythiophene, 2-ethyl-3-ethoxythiophene, 2-propyl-3-ethoxythiophene, 2- butyl-3-ethoxythiophene, 2-methyl-3-nitrothiopl1ene, 2-ethyl-3-nitrothiophene, 2-propyl-3-nitrothiophene, 2-butyl-3- nitrothiophene, 2 methyl 3 aminothiophene, 2-ethy1-3- aminothiophene, 2-pr0pyl-3 aminothiophene, 2-butyl-3- aminothiophene, 2-methy1furan, 2-ethylfuran, 2-propylfuran, 2-butylfuran, 2,3-dimethylfuran, 2,3-diethylfuran, 2,3-dipropylfuran, 2,3dibutylfuran, 2,5-dimethylfuran, 2, S-diethylfuran, 2,5-dipropylfuran, 2,5-dibutylfuran, 2,3,5- trimethylfuran, 2,3,5-triethylfuran, 2,3,5-tripropylfuran, 2,3,5-tributylfuran, 2-methyl-3-methoxyturan, 2-ethyl-3- methoxyfuran, 2-propyl-3 methoxyfuran, 2 butyl 3 methoxyfuran, 2 methyl 3 ethoxyfuran, 2 ethyl-3- ethoxyfuran, 2-propyl 3 ethoxyfuran, 2-butyl-3-ethoxyfuran, 2-ethyl-4-methoxyfuran, 2-propyl-4-methoxyfuran, 2-butyl-4-methoxyfuran, 2-ethyl-4-ethoxyturan, Z-propyl- 4-ethoxyfuran, 2-methyl-3-nitrofuran, 2-ethyl-3-nitrofuran, 2-propyl-3-nitrofuran, 2-butyl-3-nitrofuran, Z-rnethyl- 3-aminofuran, 2-ethyl-3-aminofuran, 2-propyl-3-aminofuran, 2-butyl-3-arninofuran, 2-methyl-4-nitrofuran, 2-ethyl- 4-nitrofuran, 2-propyl-4-nitrofuran, 2-butyl-4-nitrofuran, Z-rnethylpyrole, 2-ethylpyrole, 2-propylpyrole, 2-butylpyrole, 2,3-dimethylpyrole, 2,3-diethylpyrole, 2,3-dipropylpyrole, 2,3-dibutylpyrole, 2,5-dirnethylpyrole, 2,5-diethylpyrole, 2,5-dipropylpyrole, 2,5-dibutylpyrole, 2,3,5- trimethylpyrole, 2,3,5-triethylpyrole, 2,3,5-tripropylpyrol'e, 2,3,5-tributylpyrole, Z-methyl-S-methoxypyrole, 2-ethyl-3- methoxypyrole, 2-propy1 3 methoxypyrole, 2-butyl-3- methoxypyrole, 2-methyl-3-ethoxypyrole, 2-ethyl-3-ethoxypyrole, 2-propyl 3 ethoxypyrole, 2-butyl-3-ethoxypyrole, 2-ethyl 4 methoxypyrole, 2-propyl-4-methoxypyrole, 2-butyl 4 methoxypyrole, 2-ethyl 4 ethoxypyrole, 2 propyl 4 ethoxypyrole, 2-butyl-4-ethoxypyrole, 2-methyl-3-nitropyrole, 2-ethyl-3-nitropyrole, 2-propyl-3-nitropyrole, 2-butyl-3-nitropyrole, 2-methyl-3-aminopyrole, 2-ethyl-3-aminopyrole, 2-propyl-3-aminopyrole, 2-butyl-3-aminopyrole, 2-methyl-4-nitropyrole, 2-ethyl-4- 4 nitropyrole, 2-propyl-4-nitropyrole, 2-butyl-4-nitropyrole, 2methylpyran, Z-ethylpyran, 2-propylpyran, 2-butylpyran, 2,3-dimethylpyran, 2,3-diethylpyran, 2,3-dipropylpyran, 2, 3-dibutylpyran, 2,5-dirnethylpyran, 2,5-diethylpyran, 2,5- dipropylpyran, 2,5-dibutylpyran, 2,3,5-trimethylpyran, 2,3, S-triethylpyran, 2,3,5-tripropylpyran, 2,3,5-tributylpyran, 2-methyl-3-methoxypyran, 2-ethyl 3 methoxypyran, 2- propyl-3-methoxypyran, 2-butyl-3-rnethoxypyran, 2-methyl-3-ethoxypyran, 2-ethyl-3-ethoxypyran, 2-propyl-3-ethoxypyran, 2-butyl-3-ethoxypyran, 2-ethyl-4-methoxypyran, Z-propyl-4-methoxypyran, 2-butyl-4-methoxypyran, Z-ethyl-4-ethoxypyran, 2-propyl-4-ethoxypyran, 2-butyl-4-ethoxypyran, 2-rnethy1-3-nitropyran, 2ethyl-3-nitropyran, 2- propyl-3-nitropyran, Z-methyl-S-aminopyran, 2-ethyl-3- aminopyran, 2-propyl-3-aminopyran, 2-butyl-3-aminopyran, 2-methyl-4-nitropyran, 2-ethyl-4-nitropyran, 2-propyl- 4-nitropyran, 2-butyl-4-nitropyran, Z-methylpyridine, 2- ethylpyridine, 2-propylpyridine, 2-butylpyridine, 2,3-dirnethylpyridine, 2,3-diethylpyridine, 2,3-dipropylpyridine, 2,3-dibutylpyridine, 2,5-dimethylpyridine, 2,3-diethylpyridine, 2,3-dipropylpyridine, 2,3-dibutylpyridine, 2,5-dimethylpyridine, 2,5-diethylpyridine, 2,5-dipropylpyridine, 2,5-dibutylpyridine, 2,3,5-trimethylpyridine, 2,3,5-triethylpyridine, 2,3,5-tripropylpyridine, 2,3,5-tributylpyridine, 2-metnyl-3-methoxypyridine, 2-ethyl-3-methoxypyridine, 2-propyl-3-methoxypyridine, 2-butyl-3-rnethoxypyridine, 2-methyl-3-ethoxypyridine, 2 ethyl-3-ethoxypyridine, 2- propyl-3-ethoxypyridine, 2-butyl-3-ethoxypyridine, 2-ethyl-4-rnethoxypyridine, 2-propyl 4 methoxypyridine, 2- butyl-4-methoxypyridine, 2-ethyl-4-ethoxypyridine, 2-propyl-4-ethoxypyridine, 2-butyl-4-ethoxypyridine, 2-methyl- 3-nitropyridine, 2-ethyl-3-nitropyridine, 2-propyl-3-nitropyridine, 2-butyl-3-nitropyridine, 2-methyl-3-aminopyridine, 2-ethyl-3-aminopyridine, 2-propyl-3-arninopyridine, 2-butyl-3-arninopyridine, 2-methyl-4-nitropyridine, 2-ethy1-4-nitr0pyridine, 2-propyl-4-nitropyridine, 2-butyl-4-nitropyridine, Z-methylthiopyran, 2-ethylthiopyran, 2-propylthiopyran, Z-butylthiopyran, 2,3-dirnethylthiopyran, 2, 3-diethylthiopyran, 2,3-dipropylthiopyran, 2,3-dibutylthiopyran, 2,5-dirnethylthiopyran, 2,5-diethyltl1iopyran, 2,5- dipropylthiopyran, 2,5-dibutylthiopyran, 2,3,5-trimethylthiopyran, 2,3,5-triethylthiopyran, 2,3,5-tripropylthiopyran, 2,3,5-tributylthiopyran, 2-methyl-3-methoxythiopyran, 2-ethyl-3-methoxythiopyran, 2-propyl-3-methoxythiopyran, 2-butyl-3 methoxythiopyran, 2-rnethyl-3-ethoxythiopyran, 2-ethyl-3-ethoxythiopyran, 2-propyl-3-ethoKythiopyran, 2-butyl-3-ethoxythiopyran, 2-ethyl-4-methoxythiopyran, 2-pr0pyl-5-methoxytl1iopyran, 2-butyl-6-meth: oxythiopyran, 2-ethyl-4-ethoxythiopyran, 2-propyl-5-eth-. oxythiopyran, 2-butyl-6-ethoxythiopyran, 2-rnethyl-3-nitrothiopyran, Z-ethyl-S-nitrothiopyran, 2-propyl-3-nitrothiopyran,

2-butyl-3-nitrothiopyran, 2-methyl-3-aminothiopyran,

2-ethyl-3-aminothiopyran, 2-propyl-3-aminothiopyran, Z-butyl-3-aminothiopyran, 2-methyl-4-nitrothiopyran, 2-ethyl-4-nitrothiopyran, 2-propyl-4-nitrothiopyran, 2-butyl-4-nitrothiopyran, etc. It is to be understood that the aforementioned alkyl substituted heterocyclrc compounds are only representatives of the type of compounds which may be used and that the present inventron is not necessarily limited thereto.

These catalysts which may be used in the present process are those Which are capable of forming free radicals under the reaction conditions. These include peroxy compounds, containing the bivalent radical O-O--, and which are capable of inducing the condensation of the chloro substituted alkadiene or cycloalkadiene with the chloro nuclearly substituted alkyl heterocyclic compound. The organic peroxy compounds constitute a preferred class of catalyst for use in this invention and include peracetic acid, persuccinic acid, dimethyl peroxide, diethyl peroxide, dipropyl peroxide, di-t-butyl peroxide, butyryl peroxide, lauroyl peroxide, benzoyl peroxide, tetralin peroxide, urea peroxide, t-butyl perbenzoate, tbutyl hydroperoxide, methylcyclohexyl hydroperoxide, cyclohexanone peroxide, cumene hydroperoxide, etc.

Thus, organic peroxy compounds which are compounded commercially with various diluents for use as free radical generating catalysts may be used and include benzoyl peroxide compounded with calcium sulfate, benzoyl peroxide compounded with camphor, etc. Only catalytic 5 amounts (less than stoichiometric amounts) are needed. The reaction which occurs may be indicated as follows:

The reaction product may contain not only 2,3,4,5,5- pentachloro-l-(Z-thenyl)-l,3-cyclopentadiene (l) but also some of the isomeric products 1,2,3,4,5-pentachloro-5-(2- thenyl)-1,3-cyclopentadiene (II) and 1,3,4,5,5-penta' chloro-2-(2-thenyl) -1,3-cyclopentadiene (Ill).

The reaction of the present process involving the aforementioned startim materials is eitected at elevated reac- 40 tion temperatures which should be at least as high as the initial decomposition temperature of the free radical generating catalyst, such as the peroxide compound, in order to liberate and form free radicals which promote the reaction. In selecting a particular reaction temperature to. use in the process of the present invention, two considerations must be taken into account. First, suificient energy by means of heat must be supplied to the reaction system so that the reactants, namely, the chloro substituted alltadiene or the chloro substituted cycloalkadiene and the alkyl substituted heterocyclic compound, Will be activated sufliciently for condensation to take place when free radicals are generated by the catalyst. Second, free radical generating catalysts such as peroxy compounds, particularly organic peroxides, decompose at a measurable rate with time in a logarithmic function dependent upon temperature. This rate of decomposition can be and ordinarily is expressed as the half life of a peroxide at a particular temperature. For example, the half life in hours for di-t-butyl peroxide is 17.5 hours at C., 5.3 hours at C. and 1.7 hours at C. (calculated from data for the first 33% decomposition). A reaction system temperature must then be selected so that the free radical generating catalyst decomposes smoothly with the generation of free radicals at a half life which is not too long. In other words, sufiicient free radicals must be present to induce the present chain reaction to take place, and these radicals must be formed at a temperature at which the reactants are in a suitably activated state for condensation. When the half life of the free radical generating catalyst is greater than 10 hours, radicals ar not generated at a sufficient rate to cause the reaction to go forward at a detectable rate. Thus the reaction temperature may be within the range of from about 50 to about 300 C. and at least as high as the decomposition temperature of the catalyst, by which is meant a temperature such that the half life of the free radical generating catalyst is not greater than 10 hours. Since the half life for each free radical generating catalyst is different at different temperatures, the exact temperature to be utilized in a particular reaction will vary. However, persons skilled in the art are well acquainted with the half life vs. temperature data for dilferent free radical generating catalysts and thus it is within the skill of one familiar with the art to select the particular temperature needed for any particular catalyst. However, the operating temperatures generally do not exceed the decomposition temperature of the catalyst by more than about C. For example, when a free radical generating catalyst such as t-butyl perbenzoate is used, having a decomposition ternperature of approximately 115 C., the operating temperature of the process is from about 115 to about 265 C. When di-t-butyl peroxide having a decomposition temperature of about 130 C. is used, the process is run at a temperature ranging from about 130 to about 280 C. Higher reaction temperatures may be employed, but little advantage is gained if the temperature is more than the hereinbetore mentioned 150 C. higher than the decomposition temperature of the catalyst. in addition to the elevated temperatures which are utilized the reaction may also be effected at elevated pressures ranging from about 1 to about 100 atmospheres or more, the preferred operating pressure of the process being that which is required to maintain a substantial portion of the reactants in liquid phase. Pressure is not an important variable in the process of this invention. However, because of the low boiling points of some of the reactants it is necessary to utilize pressure withstanding equipment to insure liquid phase conditions. In batch type operations it is often desirable to utilize pressure withstanding equipment, to charge the reactants and catalyst to the vessel, and to pressure the vessel with 10, or 30, or 50 or more atmospheres with an inert gas such as nitrogen. This helps to insure the presence of liquid phase conditions. However, when the mole quantity of reactants is sufiicient, the pressure which they themselves generate at the temperature utilized is sufiicient to maintain the desired phase conditions. Furthermore, the concentration of the catalyst employed in this process may vary over a rather wide range but it is desirable to utilize low concentrations of catalysts such as from about 0.1% to about 10% of the total weight of the combined starting materials charged to the process. The reaction time may be within the range of from less than one minute to several hours depending upon the temperature and half life of the free radical generating catalyst. Generally speaking, contact times of at least 10 minutes are preferred.

It is also contemplated within the scope of this invention that the products obtained by condensing the chloro substituted conjugated alkadiene or chloro substituted conjugated cycloalkadiene with the alkyl heterocyclic compound may be further reacted with other dienophiles such as maleic anhydride, ethylene, bicycloheptene, bicycloheptadiene, etc., to yield other compositions of matter which are novel in structure and which will also possess insecticidal activity. For example the compound 2,3,4,5,5-pentachloro-1-(Z-thenyl) 1,3-cyclopentadiene which is prepared by condensing hexachlorocyclopentadiene with Z-methylthiophene may be further condensed with bicycloheptadiene at an elevated temperature of from about 50 to about 250 C. or more and at a pressure ranging from about 1 to about 100 atmospheres or more in a Diels-Alder manner to yield 2,3,4, 10,10 pentachloro 1 (2 thenyl) l,4,4a,5,8,8a hexahydro-1,4,5,S-dimethanonaphthalene, the latter compound also possessing insecticidal properties.

The physical properties of the present chloro alkadienic or chloro cycloalkadienic derivatives of an alkyl hetero cyclic compound, and the effects they have on entomological forms of life make them particularly desirable as aoaegzes insecticides and insect repellents, the compounds having many of the features desired for material of this purpose. They are, for example, toxic to insects which are destructive of plant life and materials normally subject to insect infestation, their toxic elfects being manifested by contact of the poison with the insect. The insecticides comprising the compounds of the present inention are thus effective against chewing as well as sucking types of insects. In addition, the compounds are sufficiently volatile so that when applied to plant life intended for subsequent human consumption, the plants when harvested and after allowing a reasonable time for evaporation of the applied insecticides therefrom retain none of the toxicant to prevent use of the plant and consumption as food. On the other hand, the compounds are of sutficient limited volatility to be retained on the insect for the time required to accomplish the toxic etfects of the compounds.

If so desired, the insecticide of the present invention may be combined with a diluent, said diluent being employed for the specific purpose of reducing the concentration of insecticides to the desired level in specific insecticide formulation. The particular formulation of active components in combination with the solvent or dispersant will depend upon its application. Compositions containing as high as 20% of active component may be preferred in some instances to allow deep penetration of the insecticides if so desired, as in the treatment of fibrous material, such as wood, for extinction of particular infestation, for example wood termites. For other purposes, the required concentration of active components in the formulation may be as low as 0.1% as, for example, in the treatment of fabrics for destroying moth larvae. in utilizing the present insecticidal compounds against most insects, a composition containing from about 0.1% to about by weight of the active component is highly eifective. The choice of the most desirable concentration depends upon the method utilized to apply the insecticidal composition to the infested article. In addition to the use of normal solvents, the insecticides may be dissolved in a suitable high boiling solvent or may be dispersed in a low molecular weight normally gaseous carrying agent such as propane, butane, the Freons, etc. The latter may be compressed and liquefied into a small bomb containing the insecticide which, upon release of pressure therefrom, vaporizes the liquid and suspends a quantity of the active component therein, thus providing a convenient spraying method of applying the insecticide.

The process of the present invention may be effected in any suitable manner and may comprise either a batch or a continuous type operation. For example, when a batch type operation is used, a quantity of the starting materials comprising a chloro substituted conjugated alkadiene or chloro substituted conjugated cycloalkadiene along with the alkyl heterocyclic compound are placed in an appropriate apparatus provided With heating and mixing means along with a catalytic amount of the organic peroxy compound. If the reaction is to be effected at atmospheric temperatures a condensation flask is sufficient. However, in the event that temperatures higher than those normally used are to be employed along with a correspondingly higher pressure the aforesaid feed stocks may be condensed by being placed in the glass liner of a rotating autoclave along with the catalyst and thereafter sealing said liner into said rotating autoclave. The desired pressure is effected by the introduction of an inert gas such as nitrogen and the apparatus is thereafter heated to the desired operating temperature. Upon completion of the desired residence time the flask or autoclave along with the contents thereof are cooled to room temperature. Any excess pressure is vented and the reaction product is cooled to room temperature. Any excess pressure is vented and the reaction product is separated from any remaining catalyst and/ or side reaction products and recovered by conventional means such as fractional distillation, crystallization, etc.

Another method of effecting the condensation reaction of the present type is by a continuous type operation. In this type of operation the starting materials comprising the chloro substituted alkadiene or chloro substituted cycloalkadiene and the alkyl heterocyclic compound are continuously charged to a reaction zone which is maintained at the proper operating conditions of temperature and pressure. These starting materials may be charged to the reaction Zone through separate lines, or if so desired, may be combined before entry into said reactor and charged thereto in a single line. The reaction zone may comprise an unpacked vessel or coil or may be lined with an adsorbent packing material such as fire brick, alumina, dehydrated bauxite and the like. The peroxy compound which acts as a catalyst may also be continuously charged to the reaction zone through separate lines in a catalytic amount per amount of starting material. After a desired residence time has elapsed the reaction product is continuously withdrawn, separated from the reactor effluent and purified by conventional means hereinbefore set forth.

If it is desired that the reaction products thus obtained are to be utilized as intermediates in the preparation of other insecticidal compositions of matter by condensing these products with other dienophiles the reaction may be effected, either in a batch type operation or in a continuous type operation, in a manner similar to that hereinbefore set forth, the only difference being that the latter reaction will proceed in a Diels-Alder manner in the absence of any catalytic matter.

Examples of reaction products which may be obtained by the condensation process of the present invention include 1- Z-thenyl) -2-chloro- 1 ,3-butadiene,

1- Z-thenyl) -2,3-dichloro- 1,3 -butadiene,

1- 2-thenyl) -2, 3 ,4-trichloro- 1 ,3-butadiene,

1- Z-furfuryl -2,3,4-trichloro-1 ,3-butadiene,

1-(2-furfuryl -2,3,4,5,6-pentachloro-1,3 -butadiene,-

1- (2-pyrrylmethyl) -2,3 ,4-trichloro-1 ,3-butadiene,

1-(2-pyridylmethyl)-2,3,4-trichloro-1,3-butadiene,

1-(2-H-a-pyranylmethy1)-2,3,4-trichlor0-1,3-butadiene,

1- 2-H-u-thi0pyranylmethyl -2,3,4-trichloro- 1,3-butadiene,

1- 3-H-B-thiopyranylmethyl) -2,3 ,4-trichloro-1 ,3-butadiene,

2, 3,4,5 ,5 -pentachloro-1 2-thenyl) -1 ,3-cyclopentadiene,

1,2,3,4,5-pentachloro-5- (2-thenyl) -1,3-cyclopentadiene,

2,3 ,4,5 ,5 -pentachloro- 1- Z-furfuryl) -1,3-cycl0pentadiene,

1,2, 3,4,5 -pentachloro-5 Z-furfuryl -1 ,3-cyclopentadiene,

2,3,4,5 ,5 -pentachioro- 1- Z-pyrrylmethyl) -1 ,3-cycl0pentadiene,

1,2,3,4,5-pentach1oro-5- (Z-pyrryl-methyl) -1,3-cyclopentadiene,

2,3,4, 5,5 -pentach1oro- 1 Z-pyridylmethyl) -1,3-cyclopentadiene,

1,2,3,4,5-pentachloro-5-(Z-pyridylmethyl) -1,3-cycl0pentadiene,

2, 3,4,5 ,5pentachloro-1- 3-thenyl 1 ,3-cyclopentadiene,

1,2,3,4,5-pentachloro-5-(3-theny1)-1,3-cyclopentadiene,

2,3 ,4,5 ,5 -pentachloro- 1- 3 -furfury1) l ,3-cyclopentadiene,

1,2,3,4,5-pentachloro-5-(3-furfuryl)-1,3-cyclopentadiene,

2,3,4,5,5-pentachloro- 1- 3-pyrry1methyl) 1 ,B-cyclopentadiene,

1,2,3 ,4,5-pentachloro-5- (3-pyrrylmethyl) -1,3-cyclopentadiene,

2,3 ,4, 5,5-pentachloro- 1- 3-pyridylmethyl 1 ,3-cyclopentadiene,

1,2, 3,4,5-pentachloro-5- 3-pyridylmethyl) -1,3-cycl0pentadiene,

2,3,4,5 ,5 -pentachloro- 1- (2-H-u-pyranylmethyl) 1 ,3-cyclopentadiene,

1,2,3 ,4,5*pentachloro-- (2-H- x-pyranylmethyl) 1,3-cyclopentadiene,

2,3,4,5 ,5 -pentachloro- 1-( 3-H-ol-pyranylmethyl) 1,3-cyclopentadiene,

1,2,3,4,5-pentachloro-5- 3-H-a-pyranylmethyl) -1,3-cyclopentadiene,

2,3,4,5 ,5 -pentachloro-1 -(4-H-u-pyranylmethyl) 1,3-cyclopentadiene,

1,2, 3,4,5 -pentachloro-5- (4-H-a-pyranylmethyl) -1,3-cyclopentadiene,

2,3 ,4,5,5-pentachloro-1 Z-H-a-ihiOPYI'ZiHYlIIlCthYl) -1 ,3-

cyclopentadiene,

1,2,3,4,5-pentachloro-5- 2-H-ot-thiopyranylmethyl) -1,3-

cyclopentadiene,

2,3,4,5,5-pentachloro-1- (3-1-1-[3-thiopyranylmethyl) 1,3-

cyclopentadiene,

1,2,3 ,4,5-pentachloro-5- 3-H-;8-thiopyranylmethyl) 1 3- cyclopentadiene,

2, 3,4,5 ,5 -pentachloro-1- (4-H-;8-thiopyranylmethyl 1 ,3-

cyclopentadiene,

1,2,3,4,5-pentachloro-5-(4-H-B-thiopyranylmethyl) -1,3-

cyclopentadiene,

etc. It is to be understood that the aforementioned reaction products are only representatives of the type of compounds which may be obtained from the present process and that this invention is not necessarily limited thereto.

The following examples are given to illustrate the process of the present invention which, however, are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

Example I In this example 29 g. (0.3 mole) of 2-methylthiophene, 164 g. (0.6 mole) of hexachlorocyclopentadiene and 8 g. of di-t-butyl peroxide was placed in the glass liner of a rotating autoclave. The liner was sealed into the autoclave and heated at a temperature in the range of from about 130 to about 140 C. for a period of about 4 hours. At the end of this time the autoclave and contents thereof were allowed to cool to room temperature and the reaction product comprising 200 g. of a clear dark amber liquid containing a small amount of hydrogen chloride was recovered. The product was distilled directly in vacuum over potassium carbonate, the cuts boiling at rom 103 to 142 C. at a pressure ranging from about 1.15 to about 1.31 mm. pressure were combined and distilled on a Minical column. The cut boiling at 116.5 C. at 0.6 mm. pressure (303 C. at 760 mm. pressure) comprising a mixture of 2,3,4,5,5-pentachloro-1-(2-thenyl)- 1,3-cyclopentadiene mixed with 1,3,4,5,5-pentachloro-1- (2-thenyl)-1,3-cyclopentadiene and 1,2,3,4,5-pentachloro- 5-(2thenyl)-1,3-cyclopentadiene was recovered. This product was analyzed with the following results.

Calcd for: C H Cl C, 35.91; H, 1.51; Cl, 53.00; S, 9.58. Found: C, 35.59; H, 1.63; Cl, 53.15; S, 9.45.

Example II In this example a mixture of 29 g. (0.3 mole) of 2- methylthiophene and 74 g. (0.6 mole) of 1,2-dichloro- 1,3-butadiene along with 8 g. (0.54 mole) of di-tbutylperoxide is heated at a temperature in the range of from of from about 130 to about 140 C. for a period of about hours. At the end of this time the reaction apparatus is allowed to cool to room temperature and the reaction product is then totaled and the desired product comprising 2-chloro-1-(2-thenyl)-1,3-butadiene is recovered.

Example 111 A mixture of 25 g. (0.3 mole) of Z-methylfuran, 74 g. (0.6 mole) of 1,2-dichloro-1,S-butadiene and 8 g. of di-tbutyl peroxide is heated at a temperature in the range of from about 130 to about 140 C .for a period of about 6 hours. At the end of this time the condensation apparatus and contents thereof are cooled to room tempera- 10 ture and the reaction product is treated in a manner similar to that set forth in Example I above. The desired product, comprising 1-chloro-1-( Z-furfuryl)-1,3-butadiene is recovered.

Example IV In this example a mixture of 25 g. of methylfuran, 164 g. of hexachlorocyclopentadiene and 8 g. of di-t-butyl peroxide is treated in a manner similar to that set forth in the above examples. At the end of the reaction time the flask and contents thereof are cooled to room temperature and the reaction product is subjected to fractional distillation. The desired product comprising a mixture of 2,3,4,5,5-pentachloro-1-(2 furfuryl)-l,3-cyclopentadiene, 1,3,4,5,5 pentachloro-2-(Z-furfuryl)-1,3cyclopentadiene and 1,2,3 ,4,5-pentach1oro-5-(2-furfuryl)-1,3 -cyclopentadiene is recovered.

Example V A mixture of 0.3 mole of Z-methylpyridine and 0.6 mole of hexachlorocyclopentadiene along with 8 g. of di-t-butyl peroxide is heated at a temperature in the range of from about to about C. for a period of about 6 hours. At the end of the desired residence time the condensation apparatus and contents thereof are allowed to cool to room temperature. The reaction product is distilled in vacuum over potassium carbonate and the desired product comprising a mixture of 2,3,4,5,5- pentachloro-l-(2-pyridylmethyl}-1,3-cyclopentadiene, 1,3, 4,5,5-pentachloro-2-(2 pyridylmethyl)-1,3-c.yclopentadi ene and l,2,3,4,5-pentachloro-5-(Z-pyridylmethyl)-1,3-cyclopentadiene is separated and recovered.

Example VI An insecticidal solution is prepared by admixing 1 g. of the reaction product obtained in Example 11 above, that is, a mixture of 2,3,4,5,5-pentachloro-1-(Z-thenyl)-1,3- cyclopentadiene, 1,2,3,4,5-pentachloro-5-(Z-thenyl) 1,3- cyclopentadiene and 1,3,4,5,5-pentachloro-2-(2-thenyl)- 1,4-cyclopentadiene with 1 cc. of benzene. The solution is admixed with 100 cc. of water using Triton X-l00 as an emulsifying agent. The solution is sprayed into a cage containing houseflies and will result in a 100% knockdown. Similar tests with solutions using the compounds set forth in Examples 11 to V above and prepared in an identical manner will show similar results.

I claim as my invention:

1. A process which comprises condensing a diene having at least one chlorine atom attached to each of a pair of doubly bonded carbon atoms and selected from the group consisting of chlorinated butadiene, pentadiene, hexadiene, cyclopentadiene and cyclohexadiene with a heterocyclic compound selected from the group consisting of alkyl thiophene, alkyl furan, and alkyl pyridine having from 1 to 4 carbon atoms in the alkyl group at a condensation temperature of from about 50 to about 300 C. in the presence of an organic peroxide catalyst, and recovering the resultant condensation product.

2. The process of claim 1 further characterized in that said catalyst is di-tbutyl peroxide.

3. The process of claim 1 further characterized in that said catalyst is dimethyl peroxide.

4. The process of claim 1 further characterized in that said diene is 1,2-dichloro-1,3-butadiene.

5. The process of claim 1 further characterized in that said diene is hexachlorocyclopentadiene.

6. The process of claim 1 further characterized in that said heterocyclic compound is Z-methylthiophene.

7. The process of claim 1 further characterized in that said heterocyclic compound is Z-methylfuran.

8. A process Which comprises condensing 1,2-dichloro- 1,3-butadiene with Z-methylthiophene in the presence of di-t-butyl peroxide at a temperature in the range of from about 130 to about C., and recovering the resultant 2-cl1loro-1-(2-thenyl)-l,3-butadiene.

9. A process which comprises condensing hexachlorocyclopentadiene with Z-methylthiophene in the presence 1. 1 of di-t-butyl peroxide at a temperature in the range of from about 130 to about 150 C., and recovering the resultant pentachloro-(2-thenyl)-1,3-cyclopentadienes.

10. A process which comprises condensing 1,2-dichloro- 1,3-butadiene with Z-methylfuran in the presence of di-tbutyl peroxide at a temperature in the range of from about 130 to about 150 C., and recovering the resultant 2-chl0rol (Z-furfuryl) -1,3-butadiene.

11. A process which comprises condensing hexachlorocyclopentadiene with Z-methylfuran in the presence of di-t-butyl peroxide at a temperature in the range of from about 130 to about 150 C., and recovering the resultant pentachloro-(Z-furfuryl)-1,3-cyclopentadienes.

12. The condensation product of a diene having at least one chlorine atom attached to each of a pair of doubly bonded carbon atoms and selected from the group consisting of chlorinated butadiene, pentadiene, hexadiene, cyclopentadiene and cyclohexadiene with a heterocyclic compound Selected from the group consisting of alkyl thiophene, alkyl furan, and alkyl pyridine having from 1 to 4 carbon atoms in the alkyl group at a condensation temperature of from about 50 to about 300 C. in the presence of an organic peroxide catalyst.

13. 2-chloro-1-(2-thenyl) -1,3-butadiene.

14. Pentachloro- (Z-thenyl) -1,3-cyc1opentadiene.

15. 2-chloro-1-(2-furfuryl) -l,3-butadiene.

16. Pentachloro-(Z-furfuryl) -1,3-cyclopentadiene.

17. Pentachloro-(Z-pyridylmethyl)-1,3-cyclopentadiene.

Israeli Patent No. 9,749, Chem. Abstracts, vol. 52, col. 1263 1958 

12. THE CONDENSATION PRODUCT OF A DIENE HAVING AT LEAST ONE CHLORINE ATOM ATATACHED TO EACH OF A PAIR OF DOUBLY BONDED CARBON ATOMS AND SELECTED FROM THE GROUP CONSISTING OF CHLORINATED BUTADIENE, PENTADIENE, HEXADIENE, CYCLOPENTADIENE AND CYCLOHEXADIENE WITH A HETEROCYCLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKYL THIOPHENE, ALKYL FURAN, AND ALKYL PYRIDINE HAVING FROM 1 TO 4 CARBON ATOMS IN THE ALKYL GROUP AT A CONDENSATION TEMPERATURE OF FROM ABOUT 50* TO ABOUT 300*C. IN THE PRESENCE OF AN ORGANIC PEROXIDE CATLAYST.
 17. PENTACHLORO-(2-PYRIDYLEMTHYL)-1,3-CYCLOPENTADIENE. 